The present invention provides the compound trans, trans-.DELTA.-damascone having the structure: ##STR4## and mixtures containing a high proportion of trans, trans-.DELTA.-damascone (more than 50%) and low proportion of cis, trans-.DELTA.-damascone having the structure: ##STR5## and a straightforward, economical process directed towards synthesizing trans, trans-.DELTA.-damascone and mixtures containing a high proportion of trans, trans-.DELTA.-damascone by means of the following reaction sequence: ##STR6## wherein X is chloro or bromo and utilization of trans, trans-.DELTA.-damascone and mixtures containing a high proportion of trans, trans-.DELTA.-damascone and low proportion of cis, trans-.DELTA.-damascone for their organoleptic properties in perfumes, perfumed articles, foodstuffs, foodstuff flavoring compositions, chewing gums, toothpastes, medicinal products, tobaccos, tobacco flavoring compositions, substitute tobaccos and substitute tobacco flavoring compositions.
In the perfumery art there is a considerable need for substituents having rose, berry, apple, green and sweet floral notes. Floral, musty, hay-tea-like, sweet and fruity notes are desirable in tobacco flavoring compositions and substitute tobacco flavoring compositions. Specifically described herein are materials having such an organoleptic profile but which do not discolor with age. Such fragrance materials have a wide utilization in the presence of these perfume compounds. A limited amount of such materials that give rise to these properties is available from natural sources but the natural materials are subject to wide variations in quality, are expensive, and are often in critically short supply. The same holds true for the use of trans, trans-.DELTA.-damascone or mixtures containing a high proportion of trans, trans-.DELTA.-damascone and low proportion of cis, trans-.DELTA.-damascone for use in tobacco or for use in tobacco substitutes.
In addition, there is a continuing search for food flavor compositions which can vary, fortify, modify, enhance, augment or otherwise improve the flavor and/or aroma of foodstuffs, medicinal products, toothpastes and chewing gums. To be satisfactory, such compositions should be stable, non-toxic and blendable with other ingredients to provide their own unique flavor and aroma nuances without detracting from the co-ingredients. Preferably, such compositions should be naturally occurring or present in natural foodstuffs so that their ingestible safety can be readily recognized. These materials should be capable of being synthesized in a simple and economical manner. The need for safe flavors in the berry fruit flavor area, especially the raspberry area, winey area, juice area (more especially, grape, tea and mimosa) is well known particularly in the ice cream and yogurt flavor areas. More specifically, there is a need for the development of non-toxic materials which can replace natural materials not readily available, having sweet, floral, damascenone-like, raspberry-like, fruity, cooked plum, grape juice-like, apple juice-like and winey aroma and flavor characteristics.
The instant invention provides the foregoing, which the prior art has heretofore failed to provide. Furthermore, nothing in the prior art shows the unexpected, unobvious and advantageous value of the compound having the structure: ##STR7## although mixtures presumed to be predominantly cis, trans-.DELTA.-damascone with minor amounts of trans, trans-.DELTA.-damascone have been produced by Ayyar, Cookson and Kagi as set forth in J. Chem. Soc., Perkin Trans. 1, 1975 (17) 1727-36 [title: "Synthesis of .alpha.-Damascone[trans-1-(2,6,6-Trimethylcyclohex-3-enyl)but-2-en-1-one] and .beta.-Damascenone[trans-1-(2,6,6-Trimethylcyclohexa-1,3-dienyl)but-2-en-1 -one]"]. The reaction sequence of the Ayyar synthesis of compositions presumed to be predominantly cis, trans-.DELTA.-damascone with minor amounts of trans, trans-.DELTA.-damascone is as follows: ##STR8## wherein the wavy line is representative of a "cis" or "trans" configuration of the methyl moiety with respect to the acetyl or oxy alkyl moiety, both of which are bonded to the cyclohexenyl moiety, the "cis" isomer presumably being the major isomer and the "trans" isomer presumably being the minor isomer in this reaction sequence.
The Ayyar, et al reference also teaches production of 3-butenoyl-4,4-dimethylcyclohexene according to the following reaction sequence: ##STR9## Ayyar, et al fails to teach the unexpected, unobvious significance attached to the trans, trans-.DELTA.-damascone as discovered in the instant invention.
On the other hand, in U.S. Pat. No. 3,956,392 at column 7 and 8 it is indicated that trans, e-1-crotonyl-2,2,6-trimethylcyclohexane (totally saturated insofar as the ring moiety is concerned) has unexpected, unobvious properties over cis, e-1-crotonyl-2,2,6-trimethylcyclohexane; e-.beta.-damascenone and e-.beta.-damascone. It is noteworthy that whereas trans, trans-.DELTA.-damascone of our invention has a sweet, floral, damascenone-like, raspberry, fruity, cooked plum, grape juice-like, apple juice-like, winey aroma and flavor character at 0.05 ppm with a threshold of 0.002 ppm, the corresponding cis, trans-.DELTA.-damascone which is presumed to be the Ayyar, et al. product has a damascenone-like, fruity, raspberry-like, rosey, spiced apple-like, tobacco, winey and clove aroma character with a damascenone, fruity, raspberry, rosey, spiced apple, tobacco, winey and tea flavor character at 0.05 ppm with a threshold of 0.005 ppm. The comparison of trans, trans-.DELTA.-damascone with cis, trans-.DELTA.-damascone, which is presumed to be the Ayyar, et al product, is much more dramatic with respect to the perfumery properties of trans, trans-.DELTA.-damascone as is shown in the examples set forth infra.
Swiss Pat. No. 537,352 issued on July 13, 1973 discloses 1(2-butenyl)cyclohexenes having the structure: ##STR10## and this Swiss Patent is abstracted in Chem. Abstracts 79:104808s.
However, none of the foregoing references discloses trans, trans-.DELTA.-damascone or mixtures containing a high percentage of trans, trans-.DELTA.-damascone and a less than 50% quantity of cis, trans-.DELTA.-damascone or their uses in food-stuffs, perfumes, perfumed articles, tobaccos and substituted tobaccos for their organoleptic properties.